Hydrocarbon sorbent materials

ABSTRACT

Sorbent polymers which are selective to taking up hydrocarbons are provided for separating hydrocarbons from fluids and taking up hydrocarbons from off of and intermixed with solid materials. The hydrocarbons may at least partially be expressed out of and recovered from the polymer by squeezing. The polymers may be re-used for picking up additional hydrocarbons. Methods for producing and using the polymers are also provided.

BACKGROUND

Absorbent and adsorbent materials are usable for removing and/orrecovering of components from water and air, or for picking up of onematerial off of another. Such sorbent materials may be placed in contactwith fluids to remove contaminants for purification of the fluids and/orrecovery of substances from the fluids. Some examples of uses forsorbent materials may include the cleaning of exhaust air emissions fromcombustion or other industrial processes, the cleaning of waste waterstreams from industrial processes, providing purified fluids, or theclean-up of accidental spills, such as oil spills.

The growth of environmental consciousness combined with anever-increasing use of petroleum products has led to a heightenedawareness of the need to promptly and effectively remediate pollutioncaused by various petroleum-based activities. Governmental regulationsare also becoming more and more restrictive, with ever increasingrequirements for cleaner air and water.

Some methods for controlling and cleaning up oil spills on water mayinclude containment with fences or booms, chemical dispersants toaccelerate natural dispersal, and removal which may include burning theoil, skimming the oil from the water surface, or collecting the oil forfurther processing. Other methods may rely on the use of coagulants andcatalysts to chemically interact with the oil, or may use absorbingmaterial such as straw. While these materials may aid in removingspilled oil from water, they fail to provide an adequate environmentallyacceptable solution which is able to confine, coagulate and controlspilled oil in a short period of time before the oil drops below thesurface of the water and forms an emulsion with the water, renderingremoval very difficult.

For collection of hydrocarbons, some of the materials used, such asorganogels, work only in confined environments where they are notsubjected to fluctuation in the medium or environmental conditions whichtend to break up bonding interactions. Some materials are unstable athigher temperatures, and therefore are not usable in exhaust streams.Still other materials, such as porous silica based products areinefficient, and inorganic nanowires are not amenable to large scaleproduction, nor are they completely reusable over extended periods oftime. Therefore, there remains a need for a sorbent material which canbe synthesized on a large scale, is low cost, reusable and is stable indifferent environmental conditions and in different mediums.

SUMMARY

This disclosure is not limited to the particular systems, devices andmethods described, as these may vary. The terminology used in thedescription is for the purpose of describing the particular versions orembodiments only, and is not intended to limit the scope.

In an embodiment, a sorbent may include cross-linked units having astructure of formula: —[XY_(n)]—_(m) wherein X comprises a multivalentC₅ to C₅₀ cycloalkyl, multivalent C₅ to C₅₀ heterocycloalkyl,multivalent C₅ to C₅₀ aryl, multivalent C₅ to C₅₀ heteroaryl, orcombinations thereof, Y comprises a divalent C₅ to C₃₀ cycloalkyl,divalent C₅ to C₃₀ heterocycloalkyl, divalent C₅ to C₃₀ aryl, divalentC₅ to C₃₀ heteroaryl, or combinations thereof; n is an integer of 2 to10; and m is an integer greater than or equal to 2.

In an embodiment, a method for synthesizing a sorbent, may includecrosslinking multivalent components to form a cross-linked compositionhaving a regular repeating structure of formula: —[XY_(n)]—_(m) whereinX is the multivalent component, Y is a cross-linking component, n is aninteger of 2 to 10, m is an integer greater than or equal to 2, and themultivalent component comprises C₅ to C₅₀ cycloalkyls, C₅ to C₅₀heterocycloalkyls, C₅ to C₅₀ aryls, or C₅ to C₅₀ heteroaryls, orcombinations thereof. In one embodiment, the cross-linking Y componentmay be a covalent bond, or a divalent component, or combinationsthereof.

In an additional embodiment, a method for preparing a sorbent mayinclude combining at least one 1,3,6,8-tetra-substituted-pyrene and4,4′-biphenyldiboronic acid bis(pinacol) at a molar ratio of about 1:2to form a first mixture, introducing a solvent to the first mixture toform a second mixture, introducing a base and a transmetallationcatalyst to the second mixture to form a third mixture, and reacting thethird mixture for a period of time sufficient for forming the sorbent inthe third mixture.

In a further embodiment, a method for extracting hydrophobic materialmay include contacting a composition containing at least one hydrophobicmaterial with a sorbent having a structure of formula —[XY_(n)]—_(m)wherein X comprises a multivalent component comprising a C₅ to C₅₀cycloalkyl, C₅ to C₅₀ heterocycloalkyl, C₅ to C₅₀ aryl, C₅ to C₅₀heteroaryl, or combinations thereof, Y comprises a divalent componentcomprising a C₅ to C₃₀ cycloalkyl, C₅ to C₃₀ heterocycloalkyl, C₅ to C₃₀aryl, C₅ to C₃₀ heteroaryl, or combinations thereof, n is an integer of2 to 10, and m is an integer greater than or equal to 2, wherein the atleast one hydrophobic material is taken up by the sorbent by at leastone of adsorption and absorption, and separating the sorbent with atleast one hydrophobic material from the composition.

In an additional embodiment, a filter for extracting at least onehydrophobic material from a fluid comprises a sorbent having a structureof formula —[XY_(n)]—_(n), wherein X comprises a multivalent componentcomprising a C₅ to C₅₀ cycloalkyl, C₅ to C₅₀ heterocycloalkyl, C₅ to C₅₀aryl, C₅ to C₅₀ heteroaryl, or combinations thereof, Y comprises adivalent component comprising a C₅ to C₃₀ cycloalkyl, C₅ to C₃₀heterocycloalkyl, C₅ to C₃₀ aryl, C₅ to C₃₀ heteroaryl, or combinationsthereof, n is an integer of 2 to 10, and m is an integer greater than orequal to 2.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 depicts a general structural representation of a sorbent polymeraccording to an embodiment.

FIG. 2 depicts a molecular representation of a sorbent polymer accordingto an embodiment.

FIG. 3 depicts a synthesis process for producing a sorbent polymeraccording to an embodiment.

FIG. 4 depicts an alternative synthesis process for producing a sorbentpolymer according to an embodiment.

DETAILED DESCRIPTION

An oil spill is generally considered as an undesired release of a liquidpetroleum hydrocarbon, or refined petroleum products into theenvironment as a result of human activity. Some of these hydrocarbonsinclude, for example, crude oil, gasoline, kerosene, diesel fuel, jetfuel, hexane, ethanol, methanol and pentane. While the term ‘oil spill’is most often used for spills in, marine areas from tankers or offshoredrilling rigs, it may also apply to accidental releases on land as well.In addition, there are also sources of oil seepage into waters and/oronto land as a result of natural features. These releases are pollutantsto the environment and may have toxic effects on the life forms whichare located in the vicinity of the release.

Attempts to control or clean up such hydrocarbon releases may be bychemical dispersion, combustion, mechanical containment, and/oradsorption, and may take weeks, months or even years to clean up.Available techniques for clean-up of hydrocarbon materials remaininadequate to solve the problem of massive spills. There remains a needfor a product which is relatively inexpensive, commercially viable,usable for a variety of materials, usable under a wide variety ofconditions, even extreme temperatures, and may be re-usable.

A hydrophobic, super-absorbent polymer is provided which selectivelyseparates hydrocarbons from hydrocarbon containing fluids, and mayreadily take-up hydrocarbons from solid surfaces and particulate matteras well. The generally selective sorption of hydrocarbons may be due toVan der Waal's, π-π interactions, and host-guest interactions. Therejection of polar liquids arises from its hydrophobicity. The polymeris a regular repeating cross-linked structure of multivalent cyclicorganic components cross-linked with divalent cyclic organic componentshaving a structure of formula —[XY_(n)]—_(n), wherein X is themultivalent component, and Y is the divalent component, n is an integerof 2 to 10, and m is an integer greater than or equal to 2. In anembodiment, n may be 2, 3 or 4.

As the central structural component, the multivalvent component may be amultivalent C₅ to C₅₀ cycloalkyl, a multivalent C₅ to C₅₀heterocycloalkyl, a multivalent C₅ to C₅₀ aryl, a multivalent C₅ to C₅₀heteroaryl, or any combination thereof. In an embodiment, themultivalent component may be the multivalent C₈ to C₅₀ polycyclic arylor multivalent C₈ to C₅₀ polycyclic heteroaryl.

The cross-linking divalent component may be any divalent C₅ to C₃₀cycloalkyl, divalent C₅ to C₃₀ heterocycloalkyl, divalent C₅ to C₃₀aryl, divalent C₅ to C₃₀ heteroaryl, or combinations thereof. In anembodiment, the cross-linking component may be the multivalent C₅ to C₃₀polycyclic aryl or multivalent C₅ to C₃₀ polycyclic heteroaryl.

A super-absorbent polymer of this type may be usable for taking uphydrophobic substances, such as hydrocarbons, from a solid surface, orfrom a granulated solid material, or from a fluid, either liquid or gas,or from combinations of such materials. The polymer may be dispersedonto the hydrophobic substances directly, may be dispersed into fluidscontaining the hydrophobic substances, or may be incorporated into afilter. The filter may be a flow-through type having a bed of polymerretained in a structural housing by fluid permeable members, or thefilter may have polymer retained on a support structure, such as amaterial or fiber mat, or incorporated into an open-cell polymer foam.The filter may be stationary in a fluid environment, or may be movedthrough a fluid bed to retrieve hydrocarbons from the fluid.

Hydrophobic absorbent polymer structures may be prepared by providingappropriate substituents on cyclic or aryl organic reactants andcross-coupling the reactants with one another or coupling withadditional reactants to provide regular repeating structure ofcross-linked multivalent components and divalent components. Examples ofcoupling reactions which may be usable for some reactants include theSuzuki Coupling and the Yamamoto-type Ullmann Cross-Coupling.

In an embodiment, a method for synthesizing a sorbent, may includecrosslinking multivalent components to form a cross-linked compositionhaving a regular repeating structure of formula: —[XY_(n)]—_(m) whereinX is the multivalent component, Y is a cross-linking component, n is aninteger of 2 to 10, m is an integer greater than or equal to 2, and themultivalent component comprises C₅ to C₅₀ cycloalkyls, C₅ to C₅₀heterocycloalkyls, C₅ to C₅₀ aryls, or C₅ to C₅₀ heteroaryls, orcombinations thereof. In one embodiment, the cross-linking Y componentmay be a covalent bond, or a divalent component, or combinationsthereof.

In an embodiment, wherein the cross-linking component may be anadditional divalent component, the multivalent component and divalentcomponent may be provided at a molar ratio of about 1:10 to about 2:1.The cross-linking may be done by contacting the multivalent componentand divalent component in the presence of a catalyst, which may be atransmetallation catalyst. In an embodiment the reactant multivalentcomponent may be pyrene, and the pyrene may be a tetra-substitutedpyrene having a substituent at each of positions 1, 3, 6 and 8. Thesubstituent may be a halogen, and in an embodiment, the halogen may bebromine. In an embodiment the reactant divalent component may be apolyphenyl, and the polyphenyl may have substituent boron groups.

In a further embodiment wherein the cross-liking component is a covalentbond, the cross-linking may be done by contacting the multivalentcomponent and a catalyst, which in some embodiments may be atransmetallation catalyst.

One configuration for such a super-absorbent polymer is shown in FIG. 1.wherein X represents the multivalent component and Y represents thedivalent component. Regular repeating triangular-patterned structures,or pentagonal or hexagonal-patterned structures are also possible, andthe pattern would be provided by the configuration of the componentsused.

The bonding of organic components to form such a net-like latticeworkstructure produces a polymer having numerous interstitial spaces thatmay be capable of accepting fluid therein. With a multiplicity of cycliccarbon components providing this structural network, the polymer may bestrongly hydrophobic, providing minimal, if any, interaction with polarsubstances (water), while having a strong affinity, or attraction forhydrocarbons (oils). Hydrocarbons may therefore be pulled into thepolymer to occupy the available space, while polar fluids may besubstantially completed omitted. This type of structural polymer wouldtherefore provide desirable characteristics for removal of hydrocarbonsfrom fluids, such as recovery of oil in an oil spill scenario.

A polymer having such a regular repeating structure which produces arelatively large amount of interstitial space and has a strong affinityfor hydrocarbons may thereby exhibit both adsorptive and absorptivecharacteristics for taking-up the hydrocarbons. Some hydrocarbons may beadsorbed to the structure, wherein the molecules adhere to the structurevia interactive bonding. The interstitial spaces, may, on the otherhand, act as a sponge, and soak-up a considerable amount of additionalhydrocarbon. This ability to absorb like a sponge also enables a largeportion of the hydrocarbons to be expressed back out of the polymer, forexample by applying pressure to the polymer to squeeze out thehydrocarbon. The polymer may then once again have free space therein forre-use of the polymer for soaking-up additional hydrocarbon. Thisre-usability may thereby provide a very cost-efficient product forretrieval of hydrocarbons.

To provide such a regular repeating ‘net-like’ structure, at least oneof, or both of the X and Y components may have at least one axis ofsymmetry. In an embodiment the X and Y components may be substantiallyplanar. In an embodiment, the X-component may be an organic compoundhaving a symmetrical structure with at least one axis of symmetry, suchas that of pyrene or phenanthrene, for example.

The X-component may also have symmetrically located bonding positionsfor the cross-linking Y component. The Y component may also be anorganic compound having a symmetrical structure with at least one axisof symmetry, such as that of a para-polyphenyl, for example.

The R may be one or more additional para-phenyl groups. In anembodiment, R may be 2, 3 or 4 phenylgroups.

The X component may be selected from, but is not limited to,cyclopentane, benzene, azulene, naphthalene, acenaphthylene,biphenylene, acenaphthene, anthracene, phenanthrene, pyrene, tetracene,triphenylene, phenanthrene, corannulene, perylene, coronene,bisanthrene, terrylene, ovalene, circumpyrene, [10]annulene,[14]annulene, [18]annulene, piperidine, oxane, thiane, pyridine, pyran,or thiopyran.

In an embodiment, the Y component may be an organic compound with two ormore phenyl connected to one another by a covalent bond, —O—, —S—, —NR—,—PR—, —POR—, C₁-C₄ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, or combinationsthereof, wherein R at each instance is —H, —OH, or C₁-C₄ alkyl. In oneembodiment, the Y component may be a polyphenyl having 2, 3, or 4 phenylgroups connected by a covalent bond.

In an alternative embodiment, the Y component may be selected from, butis not limited to phenyl, biphenyl, thiophene, bithiophene,terthiophene, benzo[c]thiophene, dibenzothiophene, naphthalene,anthracene, pyrene, terphenyl, carbazole, triphenylene, chrysene,benzanthracene, bipyridine, terpyridine, pentacene, benzofuran,dibenzofuran, benzimidazole, indene, quinoline, phenanthroline,benzothiazole, fluorene, 9,9-diarylfluorene or 9,9-dialkylfluorene orcombinations thereof.

In an embodiment wherein X is pyrene, each pyrene may be bonded to the Ycomponent at positions 1, 3, 6 and 8. In a further embodiment, wherein Yis biphenyl, each biphenyl may be bonded to X at one or more ofpositions 4 and 4′. If X is pyrene and Y is biphenyl, the polymer willhave the structure as shown in FIG. 2.

This superabsorbent pyrene-biphenyl polymer (Py-BPP) of FIG. 2 takes upover 12 times its weight in diesel fuel, and is stable at temperaturesup to about 500° C. Because of its non-polar, porous structure,hydrocarbons are able to penetrate deep into the Py-BPP and polarcompounds are substantially omitted. When placed in an oil-watermixture, the Py-BPP is able to remove essentially all of the oil fromthe water, leaving the water substantially oil free. The Py-BPP maytherefore provide an efficient material for clean-up of oil spills whichoccur in bodies of water, such as a tanker spill in the ocean. Undersome conditions, 100% of the oil may be removed from oil-water mixtures.Py-BPP would essentially function in the same manner in any fluid streamfor removal of hydrocarbons from the fluid, and is therefore usable as afluid purification material.

After picking up hydrocarbons, at least about 40% of the hydrocarbonsmay be recovered from the Py-BPP by applying pressure and squeezing thehydrocarbon from the polymer. Under some conditions, such as temperatureand type of hydrocarbons, at least about 60% of the hydrocarbons havebeen recovered from the Py-BPP by applying pressure and squeezing.Further, if heat is used during the recovery (temperatures below thevaporization or combustion temperature of the hydrocarbons), either byheating the hydrocarbon saturated Py-BPP prior to squeezing, or applyingheat during the squeezing process, at least about 90% of the picked uphydrocarbons may be recovered from the polymer. Any recoveredhydrocarbons may be re-used. In an ideal embodiment, 100% of thehydrocarbons may be recovered.

Additional hydrocarbon may be removed from the Py-BPP by immersing thepolymer in a solvent which dissolves the hydrocarbon and/or heating thePy-BPP to vaporize or burn off any hydrocarbons which will vaporize orburn at temperatures below about 500° C.

The Py-BPP may be re-used for picking up addition hydrocarbons, and maybe re-used over 100 times without showing any significant loss of itsability to pick up hydrocarbons. After use, the wet Py-BPP may be storedin containment vessels, or the wet polymer may be dried prior tostorage. Some examples of hydrocarbons which may be able to be taken upby the Py-BPP include, but are not limited to crude oil, gasoline,kerosene, diesel fuel, jet fuel, hexane, ethanol, methanol and pentane.

Since Py-BPP has been found to be stable at temperatures up to about500° C., the polymer is also usable in combustion exhausts for removinghydrocarbon contaminants from the heated exhaust stream. Py-BPP providesan effective filtering agent for removal of hydrocarbons from fluids,and also clean-up of hydrocarbon spills from solid materials as well.

The Py-BPP may be prepared by at least the following two processes: aSuzuki coupling reaction (shown in FIG. 3) of 1,3,6,8-tetrabromopyrenewith 4,4′-biphenyldiboronic acid bis(pinacol); or

a Yamamoto-type Ullmann cross-coupling reaction (shown in FIG. 4) of1,3,6,8-tetrakis-(4-bromo-phenyl)-pyrene.

As shown in FIG. 3, a Suzuki reaction is a transmetallation reactioninvolving a catalyzed coupling between an organoboronic compound andhalides. The boronic compound is activated by a base so that the boronatom enhances polarization of the organic ligand, and facilitatestransmetallation. For synthesis of Py-BPP, the 1,3,6,8-tetrabromopyrene(TBP) and 4,4′-biphenyldiboronic acid bis(pinacol) (BDPE) may be reactedwith a transmetallation catalyst in the presence of a solvent and abase. The reaction time may be from about 12 hours to about 40 hours.

With reference to FIG. 3, Ar—X represents the TBP and Ar′—B(OH)₂represents the BDPE. The first step in the reaction, starting from thepalladium catalyst, is the oxidative addition of palladium to thebromide of TBP to form the organopalladium species Ar—Pd(II)—X. Reactionwith base gives an intermediate Ar—Pd(II)—OH, which via transmetallationwith the boron-ate complex Ar—B(OH)₃ forms the organopalladium speciesAr′—Pd(II)—Ar. Reductive elimination restores the original palladiumcatalyst leading to the desired monomers Ar′—Ar. Repetition of the abovesteps leads to the super absorbent micro porous polymer Py-BPP.

Catalysts which may be used include catalysts which are capable ofcarrying out a transmetallation with a halogenated organic compound.Some transmetallation catalysts which may be used include, but are notlimited to tetrakis(triphenylphosphine)-palladium(0),tris-(dibenzylidene-acetone)-dipalladium(0),bis-(tri-t-butylphosphine)-palladium,tetrakis-(triphenylarsine)-palladium(0),dichlorobis-(triphenylphosphine)-palladium(II),benzylchlorobis-(triphenylphosphine)-palladium(II), paladacyclecatalysts, Bis(1,5-cyclooctadiene)nickel(0) or combinations thereof.

Some solvents which may be used include, but are not limited to dimethylformamide, dimethyl sulfoxide, acetonitrile, propylene carbonate,ethylene carbonate, 3-methoxypropionitrile, methoxyacetonitrile,dimethoxyethane, diethyl carbonate, diethyl ether, diethyl carbonate,dimethyl carbonate, 1,2-dimethoxy ethane, 1,3-dioxolane, methyl formate,2-methyl tetrahydrofuran, 3-methoxy-oxaziridine-2-one, sulfolane,tetrahydrofuran, or combinations thereof.

Some bases which may be used include, but are not limited to potassiumcarbonate, sodium hydride, sodium hydroxide, sodium bicarbonate,pyrrolidinopyridine, pyridine, triethylamine, tributylamine,trimethylamine, dimethylaminopyridine, diisopropylamine,diisopropylethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, sodiumhydroxide, N-ethyldiisopropylamine,N-(methylpolystyrene)-4-(methylamino)pyridine, potassiumbis(trimethylsilyl)-amide, sodium bis(trimethylsilyl)amide, potassiumtert-butoxide, lithium diisopropylamide, lithium2,2,6,6-tetramethylpiperidine, butyllithium or combinations thereof.

The Py-BPP may also be produced by the Yamamoto-type Ullmanncross-coupling reaction as illustrated in FIG. 4. In this reaction,halogenated aryls undergo a transmetallation reaction with a catalyst inthe presence of a solvent, providing a continuous combination of aryls.For synthesis of Py-BPP in accordance with an embodiment,1,3,6,8-tetrakis-(4-bromo-phenyl)-pyrene may be reacted with thetransmetallation catalyst in the presence of a solvent.

With reference to FIG. 4, Ar—X represents the1,3,6,8-tetrakis-(4-bromo-phenyl)-pyrene. The first step in thereaction, starting from the catalyst, would be an oxidative addition ofthe nickel to the 1,3,6,8-tetrakis-(4-bromo-phenyl)-pyrene to form theorganonickel species Ar—Ni—X. Reaction with additional Ni may thenremove the halogen from the 1,3,6,8-tetrakis-(4-bromo-phenyl)-pyrene toprovide an intermediate which may then react with additional1,3,6,8-tetrakis-(4-bromo-phenyl)-pyrene to form the organonickelspecies Ar′—NiX—Ar. Reductive elimination would remove the NiX leadingto the desired combinant Ar—Ar. Repetition of the above steps may yieldthe super absorbent micro porous polymer Py-BPP.

Catalysts which may be used include catalysts which are capable ofcarrying out a transmetallation with a halogenated organic compound.Some transmetallation catalysts which may be used include, but are notlimited to bis(1,5-cyclooctadiene)nickel(0)tetrakis(triphenylphosphine)-palladium(0),tris-(dibenzylidene-acetone)-dipalladium(0),bis-(tri-t-butylphosphine)-palladium,tetrakis-(triphenylarsine)-palladium(0),dichlorobis-(triphenylphosphine)-palladium(II),benzylchlorobis-(triphenylphosphine)-palladium(II), or paladacyclecatalysts, or combinations thereof.

Some solvents which may be used include, but are not limited to dimethylformamide, dimethyl sulfoxide, acetonitrile, propylene carbonate,ethylene carbonate, 3-methoxypropionitrile, methoxyacetonitrile,dimethoxyethane, diethyl carbonate, diethyl ether, diethyl carbonate,dimethyl carbonate, 1,2-dimethoxy ethane, 1,3-dioxolane, methyl formate,2-methyl tetrahydrofuran, 3-methoxy-oxaziridine-2-one, sulfolane,tetrahydrofuran, or combinations thereof.

Example 1 Synthesis of a Sorbent Polymer by Suzuki Coupling

An exemplary sorbent polymer, Py-BPP, may be synthesized from1,3,6,8-tetrabromopyrene (TBP) and 4,4′-Biphenyldiboronic acidbis(pinacol) ester (BDPE) in the presence of the catalysttetrakis(triphenylphosphine)-palladium(0) mixed at the molar ratios ofabout 1:2:0.1.

A first mixture was made by mixing 0.1 g of 1,3,6,8-tetrabromopyrene(TBP, 0.19 mmol) and 0.15 g of 4,4′-Biphenyldiboronic acid bis(pinacol)ester (BDPE, 0.38 mmol) in 20 ml of dimethyl formamide (DMF) in anitrogen atmosphere. The mixture was degassed by four freeze-pump-thawcycles to remove unwanted/excess dissolved gases such as oxygen. For thefreeze-pump-thaw cycles, the reaction vessel was evacuated and refilledwith argon or nitrogen gas. Evacuation and re-filling were repeated onemore time. The mixture was then cooled in liquid nitrogen withapplication of vacuum (5 bar) to the reaction mixture to solidify thesolvent in the reaction vessel. After complete solidification of thesolvent, the mixture was removed from the liquid nitrogen, and was movedto, and retained in a hot water (45° C.) bath until the solvent returnedto a liquid state. This process was repeated four times.

Following the degassing, 2 ml of 2M potassium carbonate (K₂CO₃) in waterand 45 mg of tetrakis(triphenylphosphine)-palladium(0) (38.9 μmol) wereadded to the mixture. The mixture was again degassed by fourfreeze-pump-thaw cycles in the manner as set forth above. The resultantmixture was purged three times with nitrogen gas. Other possible purginggases may include neon, argon, krypton, xenon, or radon, or combinationsthereof. The purged mixture was heated to, and maintained at about 150°C. in a schlenk flask for a duration of 36 hours with continuousstirring to carry out the desired reaction (the Suzuki coupling). Thistemperature and duration essentially allows for the resultant polymer toattain its desired functionality and properties.

The resultant mixture was cooled to room temperature and poured intowater to dissolve unused potassium carbonate and other salts such aspotassium bromide. The precipitate was filtered from the mixture andwashed with methanol and dichloromethane. The washed filtrate (thePy-BPP) was dried in a vacuum at approximately 0.1 bar at a temperatureof about 50° C. to about 60° C.

To ensure that there were no soluble monomers and oligomers in thedesired final product, the filtrate was purified by sequential soxhletextractions with methanol, dichloromethane, toluene and tetrahydrofuranfor about 12 hours each. Approximately 150 mg of Py-BPP was obtained asa dark green solid.

Example 2 Synthesis of a Sorbent Polymer by Yamamoto-Type UllmanCross-Coupling

An exemplary sorbent polymer, Py-BPP, may be synthesized from1,3,6,8-tetrakis-(4-bromo-phenyl)-pyrene in the presence ofbis(1,5-cyclooctadiene)nickel(0) catalyst.

A first mixture was prepared by placing 1 g (1.2 mmol) of1,3,6,8-tetrakis-(4-bromo-phenyl)-pyrene in 100 mL of solvent DMF. Thismixture was degassed by four freeze-pump-thaw cycles to removeunwanted/excess dissolved gases such as oxygen. For the freeze-pump-thawcycles, the reaction vessel was evacuated and refilled with argon ornitrogen gas. This evacuation and re-filling was repeated one additionaltime. This was followed by cooling of the mixture in liquid nitrogenwith application of vacuum (5 bar) to the reaction mixture. Thissolidified the solvent in the reaction vessel. After completesolidification of the solvent, the mixture was removed from the liquidnitrogen, and was moved to, and retained in a hot water (45° C.) bathuntil the solvent returned to a liquid state. This process was repeatedfour times.

Following the degassing, 2.25 g of bis(1,5-cyclooctadiene)nickel(0)(8.18 mmol) was added to the mixture. The mixture was again degassed byfour freeze-pump-thaw cycles as discussed above. The resultant mixturewas purged three times with nitrogen gas, followed by heating themixture to, and maintaining the mixture at about 80° C. in a schlenkflask for a duration of about 12 hours with continuous stirring to carryout the desired reaction (the Yamamoto-Ullman coupling). Thistemperature and duration may allow for the resultant polymer to attainits desired functionality and properties.

The resultant mixture was cooled to room temperature and concentratedHCl was added. The precipitate was filtered from the mixture and washedwith chloroform, tetrahydrofuran and water, respectively. The washedfiltrate (the Py-BPP) was dried in a vacuum at a pressure ofapproximately 0.1 bar at a temperature of about 50° C. to about 60° C.

Example 3 Characterization of a Sorbent Polymer

One exemplary sorbent polymer, Py-BPP, was evaluated with varioussystems to verify its structure and evaluate its functionality.

N₂ gas adsorption experiments (77 K) of the polymer (desolvated at 483K) show a typical type-I profile of the isotherms with steep uptake atlow pressure regions and a maximum N₂ uptake of 792 mL/g. This uptakeindicates the micro-porous nature of the polymer. The adsorptionisotherm also shows an increase in N₂ uptake at P/P0>0.8 (P0 is thesaturated vapor pressure of the gas at 77 K). This may be attributed tothe interparticulate porosity associated with the meso- andmacrostructures of the bulk sample.

BET (Brunauer-Emmett-Teller) evaluation of the polymer using aQuuantchrome Quadrasorb-SI analyzer showed the surface area of Py-BPP tobe about 370 m^(2/)g.

An emission spectra of Py-BPP measured with Perkin Elmer Ls55Luminescence Spectrometer showed a greenish yellow emission at about500-700 nm with a maximum emission at about 520 nm. The red-shiftedabsorption (374 nm), and emission at 520 nm of Py-BPP compared totetraphenyl pyrene (λ_(abs)=320 nm and λ_(em)=450 nm) and indicates thepresence of extended conjugation in the polymer. These resultsessentially indicate that the Py-BPP combines both the micro-porous andluminescent functionalities that are consistent with its structure.

The absorbent properties of Py-BPP were investigated with petroleumproducts such as diesel, petrol, hexane, and ethanol. The swellingbehavior of Py-BPP in petroleum products and ethanol was studied interms of the equilibrium state of swelling parameter (Q %) andequilibrium solvent content (H %) that may be calculated from the weightof dried and swollen polymers using the following equations:

H═((W_(wet)−W_(dry))/W_(wet))×100

Q=(W_(wet)/W_(dry))×100

Where Q is the equilibrium state of swelling parameter, H is theequilibrium solvent content, W_(dry) is the weight of the polymer beforeabsorbing petroleum products, and W_(wet) is the weight of the polymerafter absorbing petroleum products. The swelling parameter (Q) variedfrom 700-1100 and the solvent content (H) varied from 83-99 for thevarious petroleum products. These values indicate that Py-BPP may besuperabsorbent. The swelling process was essentially instantaneouscompared to other polymer absorbents and was stable for months.Furthermore, this process was able to be repeated many times usingrecycled Py-BPP after the desolvation process under vacuum. Themicro-pores of Py-BPP may be structurally sound for the diffusion ofsmall gas molecules, solvation results in the structural re-organizationof the aromatic framework, resulting in the observed macroscopicswelling. This instantaneous swelling is essentially unknown in othermicro-porous polymers and provides Py-BPP its ability to function as aselective absorbent material.

Example 4 Separation of Oil from a Mixture of Oil and Water

A mixture of 18 ml of commercial diesel oil and 62 ml of water was madein an open beaker (1:3.5 volume ratio). A first 500 mg of Py-BPP wasadded and oil was absorbed. An additional 500 mg of Py-BPP was added tobeaker to absorb any remaining oil so that there was a total of 100 mgof Py-BPP in the beaker. The polymer powder quickly absorbed the oil andswelled, increasing in size. The Py-BPP showed an uptake capacity of upto about 12 times its weight for the collection of oil. The swelledpolymer was scooped out leaving the water essentially without any tracesof oil. The polymer was then hand squeezed to recover oil from thepolymer. The polymer was fully recovered, and about 10 ml of oil (about55%) was recovered.

Similar phase-selective swelling and uptake by Py-BPP has been obtainedfor other oils and hydrocarbon solvents. The instantaneous swellingaction of Py-BPP allows for a convenient ambient temperature strategyfor oil recovery, without additional heating and mechanical stirringprocedures.

As used in this document, the singular forms “a,” “an,” and “the”include plural references unless the context clearly dictates otherwise.Unless defined otherwise, all technical and scientific terms used hereinhave the same meanings as commonly understood by one of ordinary skillin the art. Nothing in this disclosure is to be construed as anadmission that the embodiments described in this disclosure are notentitled to antedate such disclosure by virtue of prior invention. Asused in this document, the term “comprising” means “including, but notlimited to.”

In the above detailed description, reference is made to the accompanyingdrawings, which form a part hereof. In the drawings, similar symbolstypically identify similar components, unless context dictatesotherwise. The illustrative embodiments described in the detaileddescription, drawings, and claims are not meant to be limiting. Otherembodiments may be used, and other changes may be made, withoutdeparting from the spirit or scope of the subject matter presentedherein. It will be readily understood that the aspects of the presentdisclosure, as generally described herein, and illustrated in theFigures, can be arranged, substituted, combined, separated, and designedin a wide variety of different configurations, all of which areexplicitly contemplated herein.

The present disclosure is not to be limited in terms of the particularembodiments described in this application, which are intended asillustrations of various aspects. Many modifications and variations canbe made without departing from its spirit and scope, as will be apparentto those skilled in the art. Functionally equivalent methods andapparatuses within the scope of the disclosure, in addition to thoseenumerated herein, will be apparent to those skilled in the art from theforegoing descriptions. Such modifications and variations are intendedto fall within the scope of the appended claims. The present disclosureis to be limited only by the terms of the appended claims, along withthe full scope of equivalents to which such claims are entitled. It isto be understood that this disclosure is not limited to particularmethods, reagents, compounds, compositions or biological systems, whichcan, of course, vary. It is also to be understood that the terminologyused herein is for the purpose of describing particular embodimentsonly, and is not intended to be limiting.

With respect to the use of substantially any plural and/or singularterms herein, those having skill in the art can translate from theplural to the singular and/or from the singular to the plural as isappropriate to the context and/or application. The varioussingular/plural permutations may be expressly set forth herein for sakeof clarity.

It will be understood by those within the art that, in general, termsused herein, and especially in the appended claims (e.g., bodies of theappended claims) are generally intended as “open” terms (e.g., the term“including” should be interpreted as “including but not limited to,” theterm “having” should be interpreted as “having at least,” the term“includes” should be interpreted as “includes but is not limited to,”etc.). It will be further understood by those within the art that if aspecific number of an introduced claim recitation is intended, such anintent will be explicitly recited in the claim, and in the absence ofsuch recitation no such intent is present. For example, as an aid tounderstanding, the following appended claims may contain usage of theintroductory phrases “at least one” and “one or more” to introduce claimrecitations. However, the use of such phrases should not be construed toimply that the introduction of a claim recitation by the indefinitearticles “a” or “an” limits any particular claim containing suchintroduced claim recitation to embodiments containing only one suchrecitation, even when the same claim includes the introductory phrases“one or more” or “at least one” and indefinite articles such as “a” or“an” (e.g., “a” and/or “an” should be interpreted to mean “at least one”or “one or more”); the same holds true for the use of definite articlesused to introduce claim recitations. In addition, even if a specificnumber of an introduced claim recitation is explicitly recited, thoseskilled in the art will recognize that such recitation should beinterpreted to mean at least the recited number (e.g., the barerecitation of “two recitations,” without other modifiers, means at leasttwo recitations, or two or more recitations). Furthermore, in thoseinstances where a convention analogous to “at least one of A, B, and C,etc.” is used, in general such a construction is intended in the senseone having skill in the art would understand the convention (e.g., “asystem having at least one of A, B, and C” would include but not belimited to systems that have A alone, B alone, C alone, A and Btogether, A and C together, B and C together, and/or A, B, and Ctogether, etc.). In those instances where a convention analogous to “atleast one of A, B, or C, etc.” is used, in general such a constructionis intended in the sense one having skill in the art would understandthe convention (e.g., “a system having at least one of A, B, or C” wouldinclude but not be limited to systems that have A alone, B alone, Calone, A and B together, A and C together, B and C together, and/or A,B, and C together, etc.). It will be further understood by those withinthe art that virtually any disjunctive word and/or phrase presenting twoor more alternative terms, whether in the description, claims, ordrawings, should be understood to contemplate the possibilities ofincluding one of the terms, either of the terms, or both terms. Forexample, the phrase “A or B” will be understood to include thepossibilities of “A” or “B” or “A and B.”

In addition, where features or aspects of the disclosure are describedin terms of Markush groups, those skilled in the art will recognize thatthe disclosure is also thereby described in terms of any individualmember or subgroup of members of the Markush group.

As will be understood by one skilled in the art, for any and allpurposes, such as in terms of providing a written description, allranges disclosed herein also encompass any and all possible subrangesand combinations of subranges thereof. Any listed range can be easilyrecognized as sufficiently describing and enabling the same range beingbroken down into at least equal halves, thirds, quarters, fifths,tenths, etc. As a non-limiting example, each range discussed herein canbe readily broken down into a lower third, middle third and upper third,etc. As will also be understood by one skilled in the art all languagesuch as “up to,” “at least,” and the like include the number recited andrefer to ranges which can be subsequently broken down into subranges asdiscussed above. Finally, as will be understood by one skilled in theart, a range includes each individual member. Thus, for example, a grouphaving 1-3 cells refers to groups having 1, 2, or 3 cells. Similarly, agroup having 1-5 cells refers to groups having 1, 2, 3, 4, or 5 cells,and so forth.

Various of the above-disclosed and other features and functions, oralternatives thereof, may be combined into many other different systemsor applications. Various presently unforeseen or unanticipatedalternatives, modifications, variations or improvements therein may besubsequently made by those skilled in the art, each of which is alsointended to be encompassed by the disclosed embodiments.

1. A sorbent comprising cross-linked units having a structure offormula:—[XY_(n)]—_(m) wherein: X comprises a multivalent C₅ to C₅₀ cycloalkyl,multivalent C₅ to C₅₀ heterocycloalkyl, multivalent C₅ to C₅₀ aryl,multivalent C₅ to C₅₀ heteroaryl, or combinations thereof; Y comprises adivalent C₅ to C₃₀ cycloalkyl, divalent C₅ to C₃₀ heterocycloalkyl,divalent C₅ to C₃₀ aryl, divalent C₅ to C₃₀ heteroaryl, or combinationsthereof; n is an integer of 2 to 10; and m is an integer greater than orequal to
 2. 2. The sorbent of claim 1, wherein: n is 2, 3 or 4; thecross-linked units are substantially planar; X comprises a multivalentC₈ to C₅₀ polycyclic aryl or multivalent C₈ to C₅₀ polycyclicheteroaryl; and Y comprises a polyphenyl having 2, 3, or 4 phenylgroups. 3-10. (canceled)
 11. The sorbent of claim 1, wherein each Xcomprises cyclopentane, benzene, azulene, naphthalene, acenaphthylene,biphenylene, acenaphthene, anthracene, phenanthrene, pyrene, tetracene,triphenylene, phenanthrene, corannulene, perylene, coronene,bisanthrene, terrylene, ovalene, circumpyrene, [10]annulene,[14]annulene, [18]annulene, piperidine, oxane, thiane, pyridine, pyran,or thiopyran.
 12. The sorbent of claim 1, wherein each Y comprises twoor more phenyl groups connected by a covalent bond, —O—, —S—, —NR—,—PR—, —POR—, C₁-C₄ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, or combinationsthereof, wherein R at each instance is —H, —OH, or C₁-C₄ alkyl.
 13. Thesorbent of claim 1, wherein: X comprises pyrene and Y comprisesbiphenyl; each pyrene is bonded to a biphenyl at one or more ofpositions 1, 3, 6, and 8; and each biphenyl is bonded to X at one ormore of positions 4 and 4′.
 14. The sorbent of claim 1, having arepeating structure:


15. The sorbent of claim 1, having a repeating structure:


16. A method for synthesizing a sorbent, the method comprisingcrosslinking multivalent components to form a cross-linked compositionhaving a regular repeating structure of formula:—[XY_(n)]—_(m) wherein: X is the multivalent component; Y is across-linking component; n is an integer of 2 to 10; and m is an integergreater than or equal to
 2. 17. The method of claim 16, wherein: themultivalent component comprises C₅ to C₅₀ cycloalkyls, C₅ to C₅₀heterocycloalkyls, C₅ to C₅₀ aryls, or C₅ to C₅₀ heteroaryls, orcombinations thereof; and the cross-linking component comprises acovalent bond, a divalent component, or combinations thereof.
 18. Themethod of claim 16, wherein the cross-linking component is a divalentcomponent and the cross-linking comprises contacting the multivalentcomponent and the divalent component in the presence of atransmettalation catalyst.
 19. The method of claim 18, wherein thecatalyst is tetrakis(triphenylphosphine)-palladium(0),tris-(dibenzylidene-acetone)-dipalladium(0),bis-(tri-t-butylphosphine)-palladium,tetrakis-(triphenylarsine)-palladium(0),dichlorobis-(triphenylphosphine)-palladium(II),benzylchlorobis-(triphenylphosphine)-palladium(II), paladacyclecatalysts, Bis(1,5-cyclooctadiene)nickel(0) or combinations thereof. 20.The method of claim 18, wherein: the cross-linking comprises a SuzukiCoupling; the multivalent component comprises a pyrene having a halogenat each of positions 1, 3, 6, 8; and the divalent component comprises adivalent arylboron.
 21. The method of claim 16, wherein the multivalentcomponent is 1,3,6,8-tetrabromopyrene, the divalent component is4,4′-biphenyldiboronic acid bis(pinacol), and the cross-linkingcomprises: combining 1,3,6,8-tetrabromopyrene with4,4′-biphenyldiboronic acid bis(pinacol) at a molar ratio of about, asolvent, a base and a transmettalation catalyst to form a mixture; andforming the cross-linked composition in the mixture.
 22. The method ofclaim 21, wherein: the solvent comprises dimethyl formamide, dimethylsulfoxide, acetonitrile, propylene carbonate, ethylene carbonate,3-methoxypropionitrile, methoxyacetonitrile, dimethoxyethane, diethylcarbonate, diethyl ether, diethyl carbonate, dimethyl carbonate,1,2-dimethoxy ethane, 1,3-dioxolane, methyl formate, 2-methyltetrahydrofuran, 3-methoxy-oxaziridine-2-one, sulfolane,tetrahydrofuran, or combinations thereof; and the base comprisespotassium carbonate, sodium hydride, sodium bicarbonate,pyrrolidinopyridine, pyridine, triethylamine, tributylamine,trimethylamine, dimethylaminopyridine, diisopropylamine,diisopropylethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, sodiumhydroxide, N-ethyldiisopropylamine,N-(methylpolystyrene)-4-(methylamino)pyridine, potassiumbis(trimethylsilyl)-amide, sodium bis(trimethylsilyl)amide, potassiumtert-butoxide, lithium diisopropylamide, lithium2,2,6,6-tetramethylpiperidine, butyllithium or combinations thereof. 23.The method of claim 21, further including: combining the1,3,6,8-tetrabromopyrene and 4,4′-biphenyldiboronic acid bis(pinacol) ata molar ratio of about 1:2 to form a first mixture; introducing thesolvent to the first mixture at a molar ratio of about 680:1 solvent to4,4′-biphenyldiboronic acid bis(pinacol) to form a second mixture;introducing a base and a transmetallation catalyst to the second mixtureto form a third mixture, wherein a molar ratio of base to4,4′-biphenyldiboronic acid bis(pinacol) is about 10:1 and a molar ratioof tetrakis(triphenylphosphine)-palladium(0) to 4,4′-biphenyldiboronicacid bis(pinacol) is about 0.1:1; and reacting the third mixture for aperiod of time sufficient for forming the sorbent in the third mixture.24. The method of claim 23, wherein the cross-linking further comprises:purging the first mixture with an inert gas, or degassing the firstmixture, or combinations thereof, the inert gas comprising nitrogen,neon, argon, krypton, xenon, radon, or combinations thereof; degassingthe second mixture; degassing the third mixture and purging the thirdmixture with an inert gas comprising nitrogen, neon, argon, krypton,xenon, radon, or combinations thereof; heating the third mixture to atemperature of about 100° C. to about 160° C., or stirring the thirdmixture, or combinations thereof; performing the cross-linking for about12 hours to about 40 hours; filtering the cross-linked composition fromthe first mixture followed by at least one of: washing the cross-linkedcomposition with water, methanol, dichloromethane or any combinationthereof; purifying the cross-linked composition by a soxhlet extractionwith methanol, a soxhlet extraction with dichloromethane, a soxhletextraction with toluene, a soxhlet extraction with tetrahydrofuran, orany combination thereof; and drying the cross-linked composition in avacuum at a temperature of about 50° C. to about 60° C.
 25. The methodof claim 16, wherein: the multivalent components each comprise the samemultivalent component; and the cross-linking component comprises acovalent bond.
 26. The method of claim 25, wherein: the cross-linking isa Yamamoto-Type Ullman Cross-Coupling reaction; the multivalentcomponent is 1,3,6,8-tetrakis-(4-bromo-phenyl)-pyrene; and thecross-linking comprises contacting the1,3,6,8-tetrakis-(4-bromo-phenyl)-pyrenes in the presence of catalystbis(1,5-cyclooctadiene)nickel(0).
 27. A method for extractinghydrophobic material, the method comprising: contacting a compositioncontaining at least one hydrophobic material with a sorbent having astructure of formula —[XY_(n)]—_(m) wherein: X comprises a multivalentcomponent comprising a C₅ to C₅₀ cycloalkyl, C₅ to C₅₀ heterocycloalkyl,C₅ to C₅₀ aryl, C₅ to C₅₀ heteroaryl, or combinations thereof; Ycomprises a divalent component comprising a C₅ to C₃₀ cycloalkyl, C₅ toC₃₀ heterocycloalkyl, C₅ to C₃₀ aryl, C₅ to C₃₀ heteroaryl, orcombinations thereof; n is an integer of 2 to 10; and m is an integergreater than or equal to 2; wherein the at least one hydrophobicmaterial is taken up by the sorbent by at least one of adsorption andabsorption; and separating the sorbent with at least one hydrophobicmaterial from the composition.
 28. The method of claim 27, furthercomprising removing at least a portion of the at least one hydrophobicmaterial from the sorbent and repeating the steps of contacting,separating, and removing.
 29. The method of claim 28, wherein theremoving comprises at least one of: applying pressure to forcehydrophobic material from the sorbent, wherein at least about 60% of thehydrophobic material is removable by applying pressure; heating thesorbent and applying pressure to force hydrophobic material from thesorbent, wherein at least about 90% of the hydrophobic material isremovable by applying heat and pressure; heating the sorbent to at leastone of: vaporize the hydrophobic material and burn the hydrophobicmaterial; and immersing the sorbent in a solvent to dissolve the atleast one hydrophobic material.
 30. The method of claim 27, wherein: thecomposition containing the at least one hydrophobic material is aliquid, a gas, a solid, or a combination thereof; the at least onehydrophobic material comprises liquid hydrocarbon selected frompetroleum products, oil, gasoline, kerosene, diesel fuel, jet fuel,hexane, ethanol, methanol, pentane and combinations thereof; and themethod further comprises: removing at least a portion of the at leastone hydrophobic material from the sorbent; and repeating the steps ofcontacting, separating, and removing.
 31. The method of claim 27,wherein: the composition containing the at least one hydrophobicmaterial is a surface of a solid; the contacting comprises dispersingthe sorbent onto the surface; and the separating comprises at least oneof lifting the sorbent from the surface, dumping the sorbent off of thesurface, sweeping the sorbent from the surface, and vacuuming thesorbent from the surface.
 32. The method of claim 27, wherein: thecomposition containing at least one hydrophobic material is water of anocean or lake; the at least one hydrophobic material is crude oil; andthe method comprises: contacting the water and the at least onehydrocarbon with the sorbent; taking up the crude oil from the waterinto the sorbent; and separating the sorbent having the taken-up crudeoil from the water by at least one of: scooping the sorbent from thewater, suctioning the sorbent from the water, sedimentation anddecanting of the water from the sorbent, and filtering the sorbent fromthe water.
 33. A filter for extracting at least one hydrophobic materialfrom a fluid, the filter comprising: a sorbent having a structure offormula —[XY_(n)]—_(m) wherein: X comprises a multivalent componentcomprising a C₅ to C₅₀ cycloalkyl, C₅ to C₅₀ heterocycloalkyl, C₅ to C₅₀aryl, C₅ to C₅₀ heteroaryl, or combinations thereof; Y comprises adivalent component comprising a C₅ to C₃₀ cycloalkyl, C₅ to C₃₀heterocycloalkyl, C₅ to C₃₀ aryl, C₅ to C₃₀ heteroaryl, or combinationsthereof; n is an integer of 2 to 10; and m is an integer greater than orequal to
 2. 34. The filter of claim 33, wherein: X comprises amultivalent C₅ to C₅₀ aryl having at least one axis of symmetry; Ycomprises a para-polyphenyl having 2, 3, or 4 phenyl groups; and thesorbent has a repeating structure:


35. The filter of claim 33, wherein the sorbent has a repeatingstructure:


36. The filter of claim 33, wherein: the filter is re-usable; the filteris configured and arranged to at least one of: filter at least onehydrophobic material from a liquid; and filter at least one hydrophobicmaterial from a gas; and the method further comprises a supportstructure for retaining the sorbent, the support structure comprising atleast one of: a fiber mat having sorbent adhered thereto; an open cellpolymer foam having sorbent incorporated therein; a fabric havingsorbent adhered thereto; and a housing for retaining a bed of sorbenttherein, the housing comprising at least one fluid permeable member forflow of fluid into the housing and into contact the sorbent.